logo

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2017, 56, 7, 4057-4064
RETURN TO ISSUEPREVArticleNEXT

Synthesis, Structures, and Proton Self-Exchange Reaction of μ3-Oxido/Hydroxido Bridged Trinuclear Uranyl(VI) Complexes with Tridentate Schiff-Base Ligands

View Author Information
† Radioisotope Research Center, Osaka University, Suita 565-0871, Japan
‡ Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka 560-0043, Japan
*E-mail: [email protected]
Cite this: Inorg. Chem. 2017, 56, 7, 4057–4064
Publication Date (Web):March 10, 2017
https://doi.org/10.1021/acs.inorgchem.6b03175
Copyright © 2017 American Chemical Society
RIGHTS & PERMISSIONS
Article Views
438
Altmetric
-
Citations
9
LEARN ABOUT THESE METRICS

Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.

Read OnlinePDF (1 MB)
Get e-Alerts
Supporting Info (2)»
SUBJECTS:

Abstract

Abstract Image

New μ3-hydroxido/oxido bridged trinuclear uranyl(VI) complexes with 3,5-di-t-butyl-N-salicylidene-2-aminophenolato (dbusap2–) ligands, Et3NH[(UO2)3(μ3-OH)(dbusap)3] (Et3NH[1]) and (Et3NH)2[(UO2)3(μ3-O)(dbusap)3] ((Et3NH)2[2]) were synthesized and characterized. Single-crystal X-ray structures of both complexes were determined. The oxygen atom on μ3-hydroxido center in [1]− is sp3 hybridized with an average U–(μ3-O)–U bond angle of 109.7(5)°; the μ3-oxido atom in [2]2– is sp2 hybridized with an average U–(μ3-O)–U bond angle of 118.0(10)°. U–(μ3-O) distances in [1]− are long (average of 2.43(1) Å) compared with those in [2]2– (average of 2.23(2) Å). The optimized geometries of the [(UO2)3(μ3-OH)]5+ core in [(UO2)3(μ3-OH)(sap)3]− and the [(UO2)3(μ3-O)]4+ core in [(UO2)3(μ3-O)(sap)3]2– (where sap = N-salicylidene-2-aminophenolato) from density functional theory (DFT) calculations resemble those in [1]− and [2]2–, respectively. The U-(μ3-O) bond in [2]2– is significantly shorter than that in [1]−, because of the greater negative charge on the central μ3-oxido. A reversible structural conversion between [2]2– and [1]− was conducted by protonation and deprotonation of the μ3-oxido/hydroxido group. The activation enthalpy and entropy of the proton self-exchange reaction between [1]− and [2]2– determined from the temperature dependence of 1H NMR coalescence are ΔH⧧ = 23 ± 2 kJ mol–1 and ΔS⧧ = −77 ± 5 J K–1 mol–1.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b03175.

  • Crystallographic data for complexes Et3NH[1] and (Et3NH)2[2], atomic coordinates for optimized geometries of [(UO2)3(μ3-OH)(sap)3]− and [(UO2)3(μ3-O)(sap)3]2–, figures of IR and 1H NMR, and UV-vis spectra, trinuclear core structures and hydrogen bonding interactions for Et3NH[1] and (Et3NH)2[2], and Eyring plot of proton self-exchange reaction of Et3NH[1] and (Et3NH)2[2] (PDF)

  • X-ray crystallographic information (CIF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 10 publications.

  1. Kepeng Chen, Mushraf Hussain, Syed S. Razi, Yuqi Hou, Elif Akhuseyin Yildiz, Jianzhang Zhao, Halime Gul Yaglioglu, Mariangela Di Donato. Anthryl-Appended Platinum(II) Schiff Base Complexes: Exceptionally Small Stokes Shift, Triplet Excited States Equilibrium, and Application in Triplet–Triplet-Annihilation Upconversion. Inorganic Chemistry 2020, 59 (20) , 14731-14745. https://doi.org/10.1021/acs.inorgchem.0c01932
  2. Jagriti Singh, Dolly Yadav, Jai Deo Singh. En Route Activity of Hydration Water Allied with Uranyl (UO22+) Salts Amid Complexation Reactions with an Organothio-Based (O, N, S) Donor Base. Inorganic Chemistry 2019, 58 (8) , 4972-4978. https://doi.org/10.1021/acs.inorgchem.8b03622
  3. Yang Li, Xiao-Qing Zhu. Theoretical Prediction of Activation Free Energies of Various Hydride Self-Exchange Reactions in Acetonitrile at 298 K. ACS Omega 2018, 3 (1) , 872-885. https://doi.org/10.1021/acsomega.7b01911
  4. Sokratis T. Tsantis, Demetrios I. Tzimopoulos, Malgorzata Holynska, Spyros P. Perlepes. Oligonuclear Actinoid Complexes with Schiff Bases as Ligands—Older Achievements and Recent Progress. International Journal of Molecular Sciences 2020, 21 (2) , 555. https://doi.org/10.3390/ijms21020555
  5. Sascha T. Löffler, Karsten Meyer. Actinides. 2019,,https://doi.org/10.1016/B978-0-12-409547-2.14754-7
  6. . Reference Module in Chemistry, Molecular Sciences and Chemical Engineering. 2019,,https://doi.org/
  7. Sokratis T. Tsantis, Vlasoula Bekiari, Catherine P. Raptopoulou, Demetrios I. Tzimopoulos, Vassilis Psycharis, Spyros P. Perlepes. Dioxidouranium(IV) complexes with Schiff bases possessing an ONO donor set: Synthetic, structural and spectroscopic studies. Polyhedron 2018, 152 , 172-178. https://doi.org/10.1016/j.poly.2018.06.034
  8. Ya-Nan Ren, Wei Xu, Zhen-Xiu Si, Lin-Xia Zhou, Yue-Qing Zheng. Photocatalytic degradation of tetracycline antibiotics under visible light using uranyl isophthalate coordination polymers. Polyhedron 2018, 152 , 195-201. https://doi.org/10.1016/j.poly.2018.06.040
  9. Sourav Chatterjee, Dipankar Sukul, Priyabrata Banerjee, Jaydeep Adhikary. Phenoxazinone synthase activity of two iron(III) complexes comprising the same Schiff base ligand: Biomimetic functional model and mechanistic investigation. Inorganica Chimica Acta 2018, 474 , 105-112. https://doi.org/10.1016/j.ica.2018.01.024
  10. Ya-Nan Ren, Wei Xu, Lin-Xia Zhou, Yue-Qing Zheng. Two new uranyl complexes as visible light driven photocatalysts for degradation of tetracycline. Polyhedron 2018, 139 , 63-72. https://doi.org/10.1016/j.poly.2017.10.012

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

OOPS

You have to login with your ACS ID befor you can login with your Mendeley account.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE